Kinetics of UV Radiation-Induced Fast Collapse and Recovery in Thermally Cycled and Rehydrated Light- and Thermo- Double-Responsive Copolymer Films Probed by In Situ Neutron Reflectivity

The kinetics of UV radiation-induced fast collapse and recovery in thermally cycled and rehydrated light- and thermo- double-responsive copolymer films of poly(oligo(ethylene glycol) methyl ether methacrylate-co-6-(4-phenylazophenoxy)hexyl acrylate), abbreviated as P(OEGMA₃₀₀-co-PAHA), are probed by in situ neutron reflectivity (NR). The copolymer film is exposed to a thermal treatment starting at a temperature of 60 °C, which is well above its transition temperature (TT = 53 °C) before the temperature is rapidly decreased from 60 to 23 °C. Based on the applied protocol, the initially collapsed P(OEGMA₃₀₀-co-PAHA) film is rehydrated due to the switching of polymer chains from a more hydrophobic to a more hydrophilic state when the temperature falls below its TT. The whole rehydration process can be divided into 3 stages: D₂O absorption, chain rearrangement, and film reswelling. After rehydration, the thermally cycled P(OEGMA₃₀₀-co-PAHA) film is switched by UV irradiation via setting the UV radiation on and off. Considering the UV-induced collapse and recovery, both processes are slower than those observed in freshly hydrated films without any thermal stimulus history. Therefore, the experienced thermal history of the film should be considered in the design of sensors and detectors based on double-responsive copolymer films.